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Photochemical-mediated solid-state [2+2]-cycloaddition reactions of an unsymmetrical dibenzylidene acetone (monothiophos-dba)

Jarvis, A. G., Sparkes, H. A., Tallentire, S. E., Hatcher, L. E. ORCID:, Warren, M. R., Raithby, P. R., Allan, D. R., Whitwood, A. C., Cockett, M. C. R., Duckett, S. B., Clark, J. L. and Fairlamb, I. J. S. 2012. Photochemical-mediated solid-state [2+2]-cycloaddition reactions of an unsymmetrical dibenzylidene acetone (monothiophos-dba). CrystEngComm 14 (17) 10.1039/c2ce25480h

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A novel unsymmetrical dibenzylidene acetone (monothiophos-dba, compound 3), containing two chemically different alkene moieties, undergoes a selective photochemically-induced [2+2] cycloaddition solid-state transformation (single crystal and powder), as shown by X-ray diffraction methods. In the single crystal the rate constant for the cycloaddition reaction was determined {k = (2.3 ± 0.1) × 10−4 s−1}, with a 69% conversion attained, which compares well with a two-photon irradiation experiment using a Nd:YAG laser pumped dye laser at 605 nm radiation (66% conversion). Full conversion was attained using powdered 3 after 43 h. A similar conversion was noted between the single crystal and powder forms (59% and 66% conversion after 5 h irradiation). Irradiation of monothiophos-dba in solution using a 325 nm laser, and monitoring by 1H NMR spectroscopy, showed that no cycloaddition occurred, but exclusive photochemically-induced trans → cis isomerisation of the alkene bond connecting the unsubstituted aryl group (cis → trans isomerisation in these electron-deficient and polarised C[double bond, length as m-dash]C bonds occurs rapidly by thermal equilibration).

Item Type: Article
Date Type: Publication
Status: Published
Schools: Chemistry
Publisher: Royal Society of Chemistry
ISSN: 1466-8033
Date of Acceptance: 13 June 2012
Last Modified: 07 Nov 2022 09:52

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